A boron-containing organic compound as an OLED doping material and an organic electroluminescent device containing the same

Abstract

The present invention discloses a boron-containing organic compound as an OLED dopant material and an organic electroluminescent device containing the same, belonging to the field of semiconductor technology. The structure of the compound provided by the present invention is shown in general formula (1). The boron-containing compound of the present invention has a specific ring structure, a narrow half-width, a high fluorescence quantum yield, a high glass transition temperature and molecular thermal stability, and suitable HOMO and LUMO energy levels. When used as a green light dopant material in the light-emitting layer material of an OLED light-emitting device, the device's current efficiency, luminescent color purity, and device life are significantly improved.

Description

Technical Field

[0001] The present invention relates to the field of semiconductor technology, and in particular to a boron-containing organic compound as an OLED doping material and an organic electroluminescent device containing the same. Background Art

[0002] Traditional fluorescent doping materials, limited by early technology, can only utilize the 25% of singlet excitons formed by electrical excitation to emit light. This results in low internal quantum efficiency (maximum 25%) and external quantum efficiency generally below 5%, significantly lagging behind the efficiency of phosphorescent devices. Phosphorescent materials, due to the strong spin-orbit coupling at the heavy atom center that enhances intersystem crossing, can effectively utilize singlet and triplet excitons formed by electrical excitation to emit light, achieving a device internal quantum efficiency of 100%. However, the high cost of most phosphorescent materials, poor material stability, low color purity, and severe device efficiency roll-off have limited their application in OLEDs.

[0003] With the advent of the 5G era, higher requirements are being placed on color rendering standards. In addition to being efficient and stable, luminescent materials also need to have a narrower half-width to improve the color purity of the device's luminescent color. Fluorescent doping materials can achieve high fluorescence quantum and narrow half-width through molecular engineering. Blue fluorescent doping materials have achieved a phased breakthrough, and the half-width of boron-based materials can be reduced to below 30nm. However, research in the green light region, to which the human eye is more sensitive, has mainly focused on phosphorescent doping materials. However, their luminescent peak shape is difficult to narrow through simple methods. Therefore, to meet higher color rendering standards, it is of great significance to study efficient green fluorescent doping materials with narrow half-width.

[0004] In addition, TADF-sensitized fluorescence technology (TSF) combines TADF materials with fluorescent doping materials, using TADF materials as exciton-sensitizing media to convert triplet excitons formed by electrical excitation into singlet excitons, and transfers energy to fluorescent doping materials through long-range energy transfer of singlet excitons, which can also achieve 100% device quantum efficiency. This technology can make up for the shortcomings of insufficient exciton utilization of fluorescent doping materials, and effectively give play to the characteristics of high fluorescence quantum yield, high device stability, high color purity and low price of fluorescent doping materials, and has broad prospects in OLEDs applications.

[0005] Boron compounds with resonant structures are more likely to achieve narrow half-width luminescence. Such materials are used in TADF-sensitized fluorescence technology to achieve the preparation of devices with high efficiency and narrow half-width emission. For example, CN 107507921 A and CN110492006 A disclose a TADF material with a difference between the lowest singlet state and the lowest triplet state energy level of less than or equal to 0.2eV as the main body, and a boron-containing material as the doping luminescent layer combination technology; CN 110492005 A and CN 110492009 A disclose a luminescent layer combination scheme with an exciplex as the main body and a boron-containing material as the doping; both can achieve efficiency comparable to phosphorescence and a relatively narrow half-width. Therefore, the development of TADF-sensitized fluorescence technology based on narrow half-width boron-containing luminescent materials has unique advantages and strong potential in terms of BT.2020 display indicators. Summary of the Invention

[0006] To address the aforementioned issues with the existing technology, the present inventors have provided a boron-containing organic compound as a dopant material for OLEDs. The compound exhibits a narrow half-width (FWHM) and high fluorescence quantum yield, and can be used as a green light dopant in the emitting layer of organic electroluminescent devices (OLEDs), thereby improving the device's luminescent color purity and lifetime.

[0007] The technical solution of the present invention is as follows: a boron-containing organic compound as an OLED doping material, wherein the structure of the boron-containing organic compound is shown in general formula (1):

[0008]

[0009] In the general formula (1), Z1-Z8 are represented by CH or C-(R1) in the same or different manner each time they appear;

[0010] Each occurrence of R1 is identical or different and represents a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C6-C 30 Aryloxy, substituted or unsubstituted C6~C 30 Arylamine, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 Heteroaryl or C1-C2 containing at least one heteroatom of O, N, S, B, P, F 18 electron-withdrawing group; adjacent R1 can be connected to form a ring;

[0011] M1 ring and M2 ring are independently represented by substituted or unsubstituted C6-C 30 Aromatic ring, substituted or unsubstituted C2-C30 heteroaromatic rings;

[0012] X1, X2, X3, X4 each appear identically or differently and are represented by O, S or N-(R2);

[0013] Each occurrence of R2 is identical or different and represents a substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C1~C 10 Alkenyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C1~C 10 Aryloxy, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 Heteroaryl; R2 and R1, R2 and M1 ring and / or M2 ring may be connected to form a ring;

[0014] The substituents of the "substituted or unsubstituted" groups are selected from deuterium, tritium, halogen, C1-C 10 Alkyl, C3~C 10 Cycloalkyl, C6~C 30 Aryl, C2~C 30 Heteroaryl, C6~C 30 Aryl or C2~C 30 Heteroaryl-substituted amino, deuterium or tritium-substituted C1-C 10 Alkyl, deuterium or tritium substituted C3~C 10 Any of cycloalkyl;

[0015] The heteroatoms in the heteroaryl group and the heteroaryl ring are selected from one or more of oxygen, sulfur, boron and nitrogen atoms.

[0016] The present invention also provides an organic light-emitting device comprising a cathode, an anode and a functional layer, wherein the functional layer is located between the cathode and the anode, and is characterized in that the functional layer of the organic light-emitting device comprises the boron-containing organic compound.

[0017] The beneficial technical effects of the present invention are:

[0018] (1) The compounds of the present invention are applied to OLED devices and can be used as doping materials for light-emitting layer materials. They can emit fluorescence under the action of an electric field and can be applied to OLED lighting or OLED display fields.

[0019] (2) The compound of the present invention has a high fluorescence quantum efficiency as a doping material, and the fluorescence quantum efficiency of the material is close to 100%;

[0020] (3) The spectral FWHM of the compound of the present invention is relatively narrow, which can effectively improve the color gamut of the device and enhance the luminous efficiency of the device; BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a schematic diagram of the structure of an OLED device in which the materials listed in the present invention are applied;

[0022] Among them, 1 is a transparent substrate layer, 2 is an anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light-emitting layer, 7 is a hole blocking layer, 8 is an electron transport layer, 9 is an electron injection layer, and 10 is a cathode layer. DETAILED DESCRIPTION

[0023] The following will be combined with the accompanying drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. In the absence of conflict, the embodiments of the present invention and the features in the embodiments can be combined with each other. The following will further illustrate the present invention with reference to the accompanying drawings and specific embodiments, but it is not intended to limit the present invention.

[0024] In the present invention, unless otherwise specified, HOMO means the highest occupied molecular orbital of a molecule, and LUMO means the lowest unoccupied molecular orbital of a molecule. In addition, in the present invention, HOMO and LUMO energy levels are expressed in absolute values, and comparison between energy levels also refers to comparison of their absolute values. Those skilled in the art will appreciate that the larger the absolute value of an energy level, the lower the energy of that energy level.

[0025] In the drawings, the dimensions of layers and regions may be exaggerated for clarity. It will also be understood that when a layer or element is referred to as being "on" another layer or substrate, the layer or element may be directly on the other layer or substrate, or intervening layers may be present. Furthermore, it will be understood that when a layer is referred to as being "between" two layers, the layer may be the only layer between the two layers, or one or more intervening layers may be present. Like reference numerals refer to like elements throughout.

[0026] In the present invention, when describing electrodes, organic electroluminescent devices, and other structures, terms such as "upper," "lower," "top," and "bottom" that indicate orientation refer only to a particular state and do not imply that the structure can exist only in the described orientation. Conversely, if the structure can be repositioned, such as inverted, the orientation of the structure will change accordingly. Specifically, in the present invention, the "bottom" or "lower" side of an electrode refers to the side of the electrode that is closest to the substrate during fabrication, while the opposite side, farther from the substrate, is the "top" or "upper" side.

[0027] In the present invention, substituted or unsubstituted C6-C 30 Aryl and / or substituted or unsubstituted C2-C 30Heteroaryl refers to substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted p-terphenyl, substituted or unsubstituted m-terphenyl, substituted or unsubstituted substituted or unsubstituted triphenylene, substituted or unsubstituted perylene, substituted or unsubstituted indenyl, substituted or unsubstituted furyl, substituted or unsubstituted thienyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted triazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted oxadiazolyl, substituted or unsubstituted thiadiazolyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted unsubstituted benzimidazolyl, substituted or unsubstituted indolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenanthrazinyl, substituted or unsubstituted phenathiazinyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, combinations thereof, or fused rings of combinations thereof, but are not limited thereto.

[0028] The C1-C of the present invention 10 Alkyl (including straight-chain alkyl and branched-chain alkyl) refers to methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, sec-butyl, neopentyl, n-pentyl, isopentyl, octyl, heptyl, n-decyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1-butylpentyl, etc., but is not limited thereto.

[0029] The halogen atom mentioned in the present invention refers to a chlorine atom, a fluorine atom or a bromine atom, but is not limited thereto.

[0030] The C3-C 10 A cycloalkyl group refers to a monovalent monocyclic saturated hydrocarbon group containing 3 to 10 carbon atoms as ring atoms. In this article, a C4-C9 cycloalkyl group is preferably used, a C5-C8 cycloalkyl group is more preferably used, and a C5-C7 cycloalkyl group is particularly preferably used. Non-limiting examples thereof include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, adamantyl, and cycloheptyl.

[0031] Boron-containing organic compound represented by general formula (1):

[0032]

[0033] In the general formula (1), Z1-Z8 are represented by CH or C-(R1) in the same or different manner each time they appear;

[0034] Each occurrence of R1 is identical or different and represents a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C6-C 30 Aryloxy, substituted or unsubstituted C6~C 30 Arylamine, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 Heteroaryl or C1-C2 containing at least one heteroatom of O, N, S, B, P, F 18 electron-withdrawing group; adjacent R1 can be connected to form a ring;

[0035] M1 ring and M2 ring are independently represented by substituted or unsubstituted C6-C 30 Aromatic ring, substituted or unsubstituted C2-C 30 heteroaromatic rings;

[0036] X1, X2, X3, X4 each appear identically or differently and are represented by O, S or N-(R2);

[0037] Each occurrence of R2 is identical or different and represents a substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C1~C 10 Alkenyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C1~C 10 Aryloxy, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 Heteroaryl; R2 and R1, R2 and M1 ring and / or M2 ring may be connected to form a ring;

[0038] The substituents of the "substituted or unsubstituted" groups are selected from deuterium, tritium, halogen, C1-C 10 Alkyl, C3~C 10 Cycloalkyl, C6~C 30 Aryl, C2~C 30 Heteroaryl, C6~C 30 Aryl or C2~C 30Heteroaryl-substituted amino, deuterium or tritium-substituted C1-C 10 Alkyl, deuterium or tritium substituted C3~C 10 Any of cycloalkyl;

[0039] The heteroatoms in the heteroaryl group and the heteroaryl ring are selected from one or more of oxygen, sulfur, boron and nitrogen atoms.

[0040] In a preferred embodiment, the structure of the boron-containing organic compound is as shown in any one of the general formulas (2) to (3):

[0041]

[0042] In the general formulae (2) and (3), the definitions of Z1 to Z8, M1 ring, M2 ring, X1, X2, X3, and X4 are the same as those in the above-mentioned general formula (1).

[0043] In a preferred embodiment, the structure of the boron-containing organic compound is as shown in any one of the general formulas (1-1) to (1-6):

[0044]

[0045] In general formulas (1-1) to (1-6), the definitions of Z1-Z8, X1, X2, X3, and X4 are the same as those in the above general formula (1);

[0046] X5 and X6 are represented by O, S or N-(R3) in the same or different manner at each occurrence;

[0047] Each occurrence of R3 is identical or different and represents a substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 heteroaryl;

[0048] R a 、R b 、R c 、R d Each occurrence is represented identically or differently by deuterium, tritium, halogen, C1~C 10 Alkyl, C3~C 10 Cycloalkyl, C6~C 30 Aryl, C2~C 30 Heteroaryl, C6~C 30 Aryl or C2~C 30 Heteroaryl-substituted amino, deuterium or tritium-substituted C1-C 10 Alkyl, deuterium or tritium substituted C3~C 10 Cycloalkyl;

[0049] m, n, s, and k are independently represented as 0, 1, 2, 3, and 4;

[0050] The substituents of the "substituted or unsubstituted" groups are selected from deuterium, tritium, halogen, C1-C 10 Alkyl, C3~C 10 Cycloalkyl, C6~C 30 Aryl, C2~C 30 Heteroaryl, C6~C 30 Aryl or C2~C 30 Heteroaryl-substituted amino, deuterium or tritium-substituted C1-C 10 Alkyl, deuterium or tritium substituted C3~C 10 Any of cycloalkyl;

[0051] The heteroatoms in the heteroaryl group are selected from one or more of oxygen, sulfur, boron and nitrogen atoms.

[0052] In a preferred embodiment, the structure of the boron-containing organic compound is as shown in any one of the general formulas (4-1) to (4-8):

[0053]

[0054] In the general formulae (4-1) and (4-8), the definitions of Z1 to Z8, M1 ring, M2 ring, and R2 are the same as those in the above-mentioned general formula (1).

[0055] In a preferred embodiment, the M1 ring and the M2 ring are represented by the following ring structures:

[0056]

[0057] Asterisks indicate sites where rings can be fused.

[0058] Optimal solution, R1, R a 、R b 、R c 、R drepresented by H, deuterium, tritium, a fluorine atom, a cyano group, an adamantyl group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted diphenylamino group, a substituted or unsubstituted diphenylether group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted quinolyl, substituted or unsubstituted furyl, substituted or unsubstituted thienyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted amino, substituted or unsubstituted triazinyl, substituted or unsubstituted boryl, substituted or unsubstituted methoxy.

[0059] The M1 ring and the M2 ring are represented by a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted furan ring, a substituted or unsubstituted thiophene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted pyridine ring, or a substituted or unsubstituted quinoline ring;

[0060] R2 and R3 represent H, deuterium, tritium, a fluorine atom, an adamantyl group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted diphenylamino group, a substituted or unsubstituted diphenylether group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted benzofuranyl group, or a substituted or unsubstituted benzothienyl group.

[0061] The substituents for the above-mentioned substitutable groups are selected from deuterium, tritium, cyano, fluorine, trifluoromethyl, adamantyl, methyl, deuterated methyl, tritiated methyl, ethyl, deuterated ethyl, tritiated ethyl, isopropyl, deuterated isopropyl, tritiated isopropyl, tert-butyl, deuterated tert-butyl, tritiated tert-butyl, isobutyl, deuterated cyclopentyl, tritiated cyclopentyl, cyclopentyl, methoxy, tert-butoxy, diphenylamino, methyl-substituted diphenylamino, phenyl, deuterated benzene phenyl, tritiated phenyl, biphenyl, deuterated biphenyl, tritiated biphenyl, naphthyl, anthracenyl, phenanthrenyl, pyridyl, quinolyl, furyl, thienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, fluorine-substituted pyridyl, xanthone, cyano-substituted phenyl, cyano-substituted pyridyl, trifluoromethyl-substituted aryl, trifluoromethyl-substituted pyridyl, nitrogen-substituted terphenyl, C6-C 30 One of an aryl-substituted carbonyl, an azadimethylfluorenyl, an azadiphenylfluorenyl, a dimethylanthrone, a benzophenone, an azabenzophenone, a 9-fluorenone, an anthraquinone, a diphenylsulfone, a diphenylsulfone derivative, a diphenylborane, and a methyl-substituted furanyl.

[0062] Preferably, the specific structural formula of the boron-containing organic compound is any one of the following structures:

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072] organic electroluminescent devices

[0073] The present invention provides an organic electroluminescent device comprising a cathode, an anode and a functional layer, wherein the functional layer is located between the cathode and the anode, and is characterized in that the functional layer of the organic light-emitting device comprises a boron-containing organic compound represented by general formula (1).

[0074] In a preferred embodiment of the present invention, the functional layer includes a light-emitting layer, and the doping material of the light-emitting layer is a boron-containing organic compound represented by general formula (1).

[0075] In a preferred embodiment of the present invention, the light-emitting layer comprises a first host material, a second host material and a doping material, at least one of the first host material and the second host material is a TADF material, and at least one is a boron-containing organic compound represented by general formula (1).

[0076] Figure 1 Schematic diagram of the structure of the compound of the present invention applied to an OLED device, wherein 1 is a transparent substrate layer, 2 is an anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light-emitting layer, 7 is a hole blocking layer, 8 is an electron transport layer, 9 is an electron injection layer, and 10 is a cathode layer.

[0077] As the substrate for the organic electroluminescent device of the present invention, any substrate commonly used for organic electroluminescent devices can be used. Examples include transparent substrates such as glass or transparent plastic substrates; opaque substrates such as silicon substrates; and flexible PI film substrates. Different substrates have varying mechanical strength, thermal stability, transparency, surface smoothness, and water resistance. Depending on the properties of the substrate, its use varies. In the present invention, a transparent substrate is preferably used. The thickness of the substrate is not particularly limited.

[0078] A first electrode is formed on a substrate, and the first electrode and the second electrode may be opposite to each other. The first electrode may be an anode. The first electrode may be a transmissive electrode, a semi-transmissive electrode, or a reflective electrode. When the first electrode is a transmissive electrode, it may be formed using a transparent metal oxide, such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), or indium tin zinc oxide (ITZO). When the first electrode is a semi-transmissive electrode or a reflective electrode, it may include Ag, Mg, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, or a metal mixture. The thickness of the first electrode layer depends on the material used, and is typically 50-500 nm, preferably 70-300 nm, and more preferably 100-200 nm.

[0079] The organic functional material layer disposed between the first electrode and the second electrode includes, from bottom to top, a hole transport region, a light emitting layer and an electron transport region.

[0080] Herein, the hole transport region constituting the organic electroluminescent device can be exemplified by a hole injection layer, a hole transport layer, an electron blocking layer, and the like.

[0081] As materials for the hole injection layer, the hole transport layer, and the electron blocking layer, any material can be selected from known materials used in OLED devices.

[0082] Examples of the above materials include phthalocyanine derivatives, triazole derivatives, triarylmethane derivatives, triarylamine derivatives, oxazole derivatives, oxadiazole derivatives, hydrazone derivatives, stilbene derivatives, pyridinoline derivatives, polysilane derivatives, imidazole derivatives, phenylenediamine derivatives, amino-substituted quilone derivatives, styrylanthracene derivatives, styrylamine derivatives and other styrene compounds, fluorene derivatives, spirofluorene derivatives, silazane derivatives, aniline copolymers, porphyrin compounds, carbazole derivatives, polyarylalkane derivatives, polyphenylene vinyl and its derivatives, polythiophene and its derivatives, poly-N-vinylcarbazole derivatives, thiophene oligomers and other conductive polymer oligomers, aromatic tertiary amine compounds, styrene amination compounds, compounds, triamines, tetraamines, benzidines, propargyl diamine derivatives, p-phenylenediamine derivatives, m-phenylenediamine derivatives, 1,1'-bis(4-diarylaminophenyl)cyclohexane, 4,4'-bis(diarylamino)biphenyls, bis[4-(diarylamino)phenyl]methanes, 4,4'-bis(diarylamino)terphenyls, 4,4'-bis(diarylamino)quaterphenyls, 4,4'-bis(diarylamino)diphenyl ethers, 4,4'-bis(diarylamino)diphenylsulfanes, bis[4-(diarylamino)phenyl]dimethylmethanes, bis[4-(diarylamino)phenyl]-bis(trifluoromethyl)methanes, or 2,2-diphenylethylene compounds.

[0083] Furthermore, depending on the device configuration requirements, the hole transport film layer between the hole transport auxiliary layer and the hole injection layer of the organic electroluminescent device can be a single film layer or a stacked structure of multiple hole transport materials. In this article, the thickness of the various hole carrier conductive film layers with different functions described above is not particularly limited.

[0084] The hole injection layer contains a host organic material that can conduct holes, and also contains a P-type dopant material with a deep HOMO energy level (the corresponding LUMO energy level will also be very deep). Based on empirical summary, in order to achieve smooth hole injection from the anode to the organic film layer, the HOMO energy level of the host organic material used in the anode interface buffer layer must have certain characteristics with the P-doped material. Only then can the charge transfer state between the host material and the dopant material be achieved, and ohmic contact between the buffer layer and the anode can be achieved, achieving efficient injection and conduction of holes from the electrode.

[0085] In view of the above empirical summary, for hole-type host materials with different HOMO energy levels, different P-doped materials need to be selected to match them in order to achieve ohmic contact at the interface and improve the hole injection effect.

[0086] Therefore, in one embodiment of the present invention, in order to better inject holes, the hole injection layer further includes a P-type dopant material with charge conductivity selected from the following: quinone derivatives, such as tetracyanoquinodimethane (TCNQ) and 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinodimethane (F4-TCNQ); or hexaazatriphenylene derivatives, such as 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN); or cyclopropane derivatives, such as 4,4',4"-((1E,1'E,1"E)-cyclopropane-1,2,3-trimethylenetris(cyanoformylidene))tris(2,3,5,6-tetrafluorobenzyl); or metal oxides, such as tungsten oxide and molybdenum oxide, but not limited thereto.

[0087] In the hole injection layer of the present invention, the ratio of the hole transport material to the P-type doping material is 99:1-95:5, preferably 99:1-97:3, based on mass.

[0088] The thickness of the hole injection layer of the present invention may be 5-100 nm, preferably 5-50 nm, and more preferably 5-20 nm, but the thickness is not limited to this range.

[0089] The thickness of the hole transport layer of the present invention may be 5 to 200 nm, preferably 10 to 150 nm, and more preferably 20 to 100 nm, but the thickness is not limited to this range.

[0090] The thickness of the electron blocking layer of the present invention may be 1-20 nm, preferably 5-10 nm, but the thickness is not limited to this range.

[0091] After forming the hole injection layer, the hole transport layer and the electron blocking layer, a corresponding light emitting layer is formed on the electron blocking layer.

[0092] The light-emitting layer may include a host material and a dopant material. The host material may be a common green light host material in the art, and the dopant material may be a boron-containing organic compound represented by the general formula (1) of the present invention.

[0093] In the light-emitting layer of the present invention, the ratio of the host material to the dopant material used is 99:1-70:30, preferably 99:1-85:15 and more preferably 97:3-87:13, based on mass.

[0094] The thickness of the light-emitting layer can be adjusted to optimize the luminous efficiency and driving voltage. The preferred thickness range is 5 nm to 50 nm, more preferably 10-50 nm, and more preferably 15-30 nm, but the thickness is not limited to this range.

[0095] In the present invention, the electron transport region may include, from bottom to top, a hole blocking layer, an electron transport layer, and an electron injection layer disposed on the light emitting layer, but is not limited thereto.

[0096] The hole blocking layer is a layer that blocks the holes injected from the anode from passing through the light-emitting layer and entering the cathode, thereby extending the life of the device and improving the performance of the device. The hole blocking layer of the present invention can be arranged on the light-emitting layer. As the hole blocking layer material of the organic electroluminescent device of the present invention, compounds with hole blocking effects known in the prior art can be used, for example, phenanthroline derivatives such as bathocuproine (called BCP), metal complexes of hydroxyquinoline derivatives such as aluminum (III) bis (2-methyl-8-quinolinol) -4-phenylphenolate (BAlq), various rare earth complexes, oxazole derivatives, triazole derivatives, triazine derivatives, 9,9'-(5-(6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)-1,3-phenylene)bis(9H-carbazole) (CAS No.: 1345338-69-3 ) and other pyrimidine derivatives, etc. The thickness of the hole blocking layer of the present invention may be 2-200 nm, preferably 5-150 nm and more preferably 10-100 nm, but the thickness is not limited to this range.

[0097] The electron transport layer can be disposed on the light-emitting layer or (if present) the hole blocking layer. The electron transport layer material is a material that readily accepts electrons from the cathode and transfers the received electrons to the light-emitting layer. Preferably, the material has a high electron mobility. As the electron transport layer of the organic electroluminescent device of the present invention, electron transport layer materials for organic electroluminescent devices known in the prior art can be used, for example, metal complexes of hydroxyquinoline derivatives represented by Alq3, BAlq and Liq, various rare earth metal complexes, triazole derivatives, 2,4-bis(9,9-dimethyl-9H-fluoren-2-yl)-6-(naphthalene-2-yl)-1,3,5-triazine (CAS No.: 1459162-51-6) and other triazine derivatives, 2-(4-(9,10-di(naphthalene-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (CAS No.: 561064-11-7, commonly known as LG201) and other imidazole derivatives, oxadiazole derivatives, thiadiazole derivatives, carbodiimide derivatives, quinoxaline derivatives, phenanthroline derivatives, silicon-based compound derivatives, etc. The thickness of the electron transport layer of the present invention may be 10-80 nm, preferably 20-60 nm, and more preferably 25-45 nm, but the thickness is not limited to this range.

[0098] The electron injection layer may be provided above the electron transport layer. The electron injection layer material is generally preferably a material having a low work function so that electrons are easily injected into the organic functional material layer. As the electron injection layer material of the organic electroluminescent device of the present invention, the electron injection layer materials for organic electroluminescent devices known in the prior art can be used, for example, lithium; lithium salts such as 8-hydroxyquinoline lithium, lithium fluoride, lithium carbonate or lithium azide; or cesium salts such as cesium fluoride, cesium carbonate or cesium azide. The thickness of the electron injection layer of the present invention may be 0.1-5 nm, preferably 0.5-3 nm and more preferably 0.8-1.5 nm, but the thickness is not limited to this range.

[0099] The second electrode may be disposed above the electron transport region. The second electrode may be a cathode. The second electrode may be a transmissive electrode, a semi-transmissive electrode, or a reflective electrode. When the second electrode is a transmissive electrode, the second electrode may include, for example, Li, Yb, Ca, LiF / Ca, LiF / Al, Al, Mg, BaF, Ba, Ag, or a compound or mixture thereof; when the second electrode is a semi-transmissive electrode or a reflective electrode, the second electrode may include, but is not limited to, Ag, Mg, Yb, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF / Ca, LiF / Al, Mo, Ti, or a compound or mixture thereof. The thickness of the cathode depends on the material used and is typically 10-50 nm, preferably 15-20 nm.

[0100] The organic electroluminescent device of the present invention may further include an encapsulation structure. The encapsulation structure may be a protective structure that prevents foreign substances, such as moisture and oxygen, from entering the organic layer of the organic electroluminescent device. The encapsulation structure may be, for example, a can, such as a glass or metal can, or a thin film covering the entire surface of the organic layer.

[0101] The method for preparing an organic electroluminescent device of the present invention comprises sequentially laminating an anode, a hole injection layer, a hole transport layer, an electron blocking layer, an organic film layer, an electron transport layer, an electron injection layer, and a cathode, and optionally a cover layer, on a substrate. In this regard, vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing, or LITI methods can be used, but are not limited thereto. In the present invention, vacuum evaporation is preferably used to form the various layers. Those skilled in the art can conventionally select the various process conditions in the vacuum evaporation method according to actual needs.

[0102] The following examples are intended to better explain the present invention, but the scope of the present invention is not limited thereto.

[0103] The raw materials involved in the synthesis examples of the present invention can be purchased from the market or prepared by conventional preparation methods in the art;

[0104] Example 1 Synthesis of Compound 1:

[0105]

[0106]

[0107] (1) Preparation of intermediate M-1:

[0108] 10mmol of raw material A-1 and 22mmol of raw material B-1 were added to a three-necked flask and dissolved with a mixed solvent (70mL of toluene, 35mL of ethanol). Then, 0.1mmol of Pd(PPh3)4 and 15mL of a 3mol / L aqueous solution of K2CO3 were added and the reaction was heated under reflux for 12 hours under nitrogen protection. The sampling point plate was taken to confirm that the reaction was complete. After cooling to room temperature, the reaction mixture was filtered through a diatomaceous earth pad, rinsed with chloroform, and the resulting filtrate was evaporated in vacuo. The obtained residue was purified by column chromatography on silica gel using hexane / toluene as eluent to obtain intermediate M-1. LC-MS: Measured value: 595.16 ([M+H] + ), theoretical value: 594.28.

[0109] (2) Preparation of intermediate N-1:

[0110] In a three-necked flask, under nitrogen protection, 10 mmol of intermediate M-1, 22 mmol of raw material C-1, and 150 ml of toluene were added and stirred. Then, 0.05 mmol of Pd2(dba)3, 0.05 mmol of P(t-Bu)3, and 30 mmol of sodium tert-butoxide were added. The mixture was heated to 110°C and refluxed for 24 hours. The mixture was naturally cooled to room temperature, filtered, and the filtrate was subjected to vacuum rotary evaporation. The crude product was purified by silica gel column chromatography (eluent: hexane / CH2Cl2 = 5 / 1) to obtain the target product, intermediate N-1. LC-MS: Measured value: 747.26 ([M+H] + ), theoretical value: 746.34.

[0111] (3) Preparation of Compound 1:

[0112] In a three-necked flask, under nitrogen, 2 mmol of boron tribromide and 1 mmol of intermediate N-1 were dissolved in 30 mL of 1,2,4-trichlorobenzene. After stirring at 180°C for 20 hours, the reaction mixture was diluted with dichloromethane (50 mL) and 100 mL of pH 6 sodium phosphate buffer was added at 0°C. The aqueous layer was separated and extracted with dichloromethane (100 mL, three times). The crude product was purified by silica gel column chromatography (eluent: hexane / CH2Cl2 = 5 / 1) to obtain the desired product, Compound 1.

[0113] Example 2 Synthesis of Compound 50:

[0114]

[0115]

[0116] (1) Preparation of intermediate a-1:

[0117] In a three-necked flask, under nitrogen protection, 12 mmol of raw material D-1, 10 mmol of raw material E-1, and 150 ml of toluene were added and stirred. Then, 0.05 mmol of Pd2(dba)3, 0.05 mmol of P(t-Bu)3, and 30 mmol of sodium tert-butoxide were added. The mixture was heated to 110°C and refluxed for 24 hours. The mixture was naturally cooled to room temperature, filtered, and the filtrate was subjected to vacuum rotary evaporation. The crude product was purified by silica gel column chromatography (eluent: hexane / CH2Cl2 = 5 / 1) to obtain the target product, intermediate a-1. LC-MS: Measured value: 336.19 ([M+H] + ), theoretical value: 335.05.

[0118] (2) Preparation of intermediate b-1:

[0119] In a three-necked flask, under nitrogen protection, 3 mmol of intermediate a-1, 6 mmol of pinacol diboronate, 9 mmol of potassium acetate, 0.6 mmol of S-phos, and 0.12 mmol of Pd2(dba)3 were added to 150 mL of dioxane and refluxed for 8 h. The reaction system was cooled to room temperature, and the reaction mixture was diluted with ethyl acetate, washed with water, dried over anhydrous magnesium sulfate, and distilled under reduced pressure. The product was purified by silica gel column chromatography using n-heptane / ethyl acetate (9:1) as the eluent to obtain intermediate b-1. LC-MS: Measured value: 428.23 ([M+H] + ), exact mass: 427.18.

[0120] (3) Preparation of intermediate M-2:

[0121] 10mmol of raw material A-1 and 22mmol of intermediate b-1 were added to a three-necked flask and dissolved with a mixed solvent (70mL of toluene, 35mL of ethanol). 0.1mmol of Pd(PPh3)4 and 15mL of a 3mol / L aqueous solution of K2CO3 were then added and heated under reflux for 12 hours under nitrogen protection. The sample point plate was taken to confirm that the reaction was complete. After cooling to room temperature, the reaction mixture was filtered through a diatomaceous earth pad, rinsed with chloroform, and the resulting filtrate was evaporated in vacuo. The obtained residue was purified by column chromatography on silica gel using hexane / toluene as eluent to obtain intermediate M-2. LC-MS: Measured value: 707.35 ([M+H] + ), theoretical value: 706.22.

[0122] (4) Preparation of intermediate N-2:

[0123] In a three-necked flask, under nitrogen protection, 10 mmol of intermediate M-2, 22 mmol of raw material C-1, and 150 ml of toluene were added and stirred. Then, 0.05 mmol of Pd2(dba)3, 0.05 mmol of P(t-Bu)3, and 30 mmol of sodium tert-butoxide were added. The mixture was heated to 110°C and refluxed for 24 hours. The mixture was naturally cooled to room temperature, filtered, and the filtrate was subjected to vacuum rotary evaporation. The crude product was purified by silica gel column chromatography (eluent: hexane / CH2Cl2 = 5 / 1) to obtain the target product, intermediate N-2. LC-MS: Measured value: 859.07 ([M+H] + ), theoretical value: 858.29.

[0124] (5) Preparation of Compound 50:

[0125] In a three-necked flask, under nitrogen, 2 mmol of boron tribromide and 1 mmol of intermediate N-2 were dissolved in 30 mL of 1,2,4-trichlorobenzene. After stirring at 180°C for 20 hours, the reaction mixture was diluted with dichloromethane (50 mL) and 100 mL of pH 6 sodium phosphate buffer was added at 0°C. The aqueous layer was separated and extracted with dichloromethane (100 mL, three times). The crude product was purified by silica gel column chromatography (eluent: hexane / CH2Cl2 = 5 / 1) to obtain the desired product, Compound 50.

[0126] Example 3 Synthesis of Compound 57:

[0127]

[0128] The preparation method of compound 57 is the same as that of Example 2, except that the intermediate a-1 is replaced by the raw material B-2 to obtain the intermediate b-2. LC-MS: Measured value: 482.25 ([M+H] + ), theoretical value: 481.32; intermediate b-1 was replaced by intermediate b-2 to obtain intermediate M-3, LC-MS: measured value: 815.36 ([M+H] + ), theoretical value: 814.50; intermediate M-2 was replaced by intermediate M-3 to obtain intermediate N-3, LC-MS: measured value: 967.42 ([M+H] + ), theoretical value: 966.56; intermediate N-2 was replaced by intermediate N-3 to obtain the target product compound 57.

[0129] Example 4 Synthesis of Compound 72:

[0130]

[0131]

[0132] The preparation method of compound 72 was the same as that of Example 2, except that the intermediate a-1 was replaced by the raw material B-3 to obtain the intermediate b-3. LC-MS: Measured value: 404.08 ([M+H] + ), theoretical value: 403.27; intermediate b-1 was replaced by intermediate b-3 to obtain intermediate M-4, LC-MS: measured value: 659.34 ([M+H] + ), theoretical value: 658.40; intermediate M-4 was used to replace intermediate M-2 to obtain intermediate N-4, LC-MS: measured value: 811.29 ([M+H] + ), theoretical value: 810.47; intermediate N-2 was replaced by intermediate N-4 to obtain the target product compound 72.

[0133] Example 5 Synthesis of Compound 77:

[0134]

[0135] The preparation method of compound 77 is the same as that of Example 2, except that the intermediate a-1 is replaced by the raw material B-4 to obtain the intermediate b-4. LC-MS: Measured value: 386.14 ([M+H] + ), theoretical value: 385.22; using raw material A-2 to replace raw material A-1, using intermediate b-4 to replace intermediate b-1, to obtain intermediate M-5, LC-MS: measured value: 623.40 ([M+H] + ), theoretical value: 622.31; intermediate M-5 was used to replace intermediate M-2 to obtain intermediate N-5, LC-MS: measured value: 775.18 ([M+H] + ), theoretical value: 774.37; intermediate N-2 was replaced by intermediate N-5 to obtain the target product compound 77.

[0136] Example 6 Synthesis of Compound 95:

[0137]

[0138] The preparation method of compound 95 was the same as that of Example 2, except that raw material A-2 was used instead of raw material A-1 to obtain intermediate M-6. LC-MS: measured value: 707.17 ([M+H] + ), theoretical value: 706.22; intermediate M-2 was replaced by intermediate M-6 to obtain intermediate N-6, LC-MS: measured value: 859.21 ([M+H] + ), theoretical value: 858.29; intermediate N-2 was replaced by intermediate N-6 to obtain the target product compound 95.

[0139] Example 7 Synthesis of Compound 98:

[0140]

[0141]

[0142] The preparation method of compound 98 was the same as that of Example 3, except that raw material A-2 was used instead of raw material A-1 to obtain intermediate M-7. LC-MS: measured value: 815.42 ([M+H] + ), theoretical value: 814.50; intermediate M-3 was replaced by intermediate M-7 to obtain intermediate N-7, LC-MS: measured value: 967.37 ([M+H] + ), theoretical value: 966.56; intermediate N-3 was replaced by intermediate N-7 to obtain the target product compound 98.

[0143] Example 8 Synthesis of Compound 117:

[0144]

[0145] The preparation method of compound 117 was the same as that of Example 3, except that raw material A-3 was used instead of raw material A-1 to obtain intermediate M-8. LC-MS: measured value: 817.35 ([M+H] + ), theoretical value: 816.47; intermediate M-8 was used to replace intermediate N-3 to obtain the target product compound 117.

[0146] Example 9 Synthesis of Compound 154:

[0147]

[0148]

[0149] The preparation method of compound 154 was the same as that of Example 2, except that the intermediate a-1 was replaced by the raw material B-5 to obtain the intermediate b-5. LC-MS: Measured value: 297.04 ([M+H] + ), theoretical value: 296.16; intermediate A-2 was used to replace intermediate A-1, and intermediate b-5 was used to replace intermediate b-1 to obtain intermediate M-9, LC-MS: measured value: 445.33 ([M+H] + ), theoretical value: 444.18; intermediate M-9 was used to replace intermediate M-2, and raw material C-2 was used to replace raw material C-1 to obtain intermediate N-9, LC-MS: measured value: 709.15 ([M+H] + ), theoretical value: 708.37; intermediate N-2 was replaced by intermediate N-9 to obtain the target product compound 154.

[0150] The structural characteristics of the compounds obtained in each example are shown in Table 1

[0151] Table 1

[0152]

[0153] The compounds of the present invention can be used in light-emitting devices as doping materials for light-emitting layers. The physical and chemical properties of the compounds prepared in the above embodiments of the present invention were tested, and the test results are shown in Table 2:

[0154] Table 2

[0155]

[0156] Note: Glass transition temperature (Tg) was determined by differential scanning calorimetry (DSC, DSC204F1 differential scanning calorimeter from NETZSCH, Germany) at a heating rate of 10°C / min. The thermal gravimetric temperature (Td) is the temperature at which the weight loss reaches 1% in a nitrogen atmosphere, measured on a TGA-50H thermogravimetric analyzer from Shimadzu Corporation, Japan, with a nitrogen flow rate of 20 mL / min. The highest occupied molecular orbital (HOMO) energy level was determined using an ionization energy measurement system (IPS-3) in a nitrogen environment. Eg was determined using a dual-beam UV-visible spectrophotometer (Model: TU-1901), where LUMO = HOMO + Eg. PLQY (fluorescence quantum yield) and FWHM (full width at half maximum) were measured in thin films using a Horiba Fluorolog-3 series fluorescence spectrometer.

[0157] As can be seen from the data in the table above, the compounds of the present invention have high glass transition temperatures and decomposition temperatures. When used as dopants in the light-emitting layer, they can inhibit the crystallization and film phase separation of the material; they can also inhibit the decomposition of the material at high brightness, thereby improving the device's operating life. Furthermore, the compounds of the present application have shallow HOMO energy levels. When added as dopants to the host material, they can help suppress the generation of carrier traps, improve the host-guest energy transfer efficiency, and thus enhance the device's luminous efficiency.

[0158] The compound of the present invention has a high fluorescence quantum efficiency as a doping material, and the fluorescence quantum efficiency of the material is close to 100%; at the same time, the spectral FWHM of the material is narrow, which can effectively improve the color gamut of the device and improve the luminous efficiency of the device; finally, the evaporation decomposition temperature of the material is high, which can inhibit the evaporation decomposition of the material and effectively improve the life of the device.

[0159] The following describes in detail the application effects of the OLED materials synthesized by the present invention in devices using device Examples 1-9 and Comparative Examples 1-3. The device fabrication processes for Device Examples 2-9 and Comparative Examples 1-3 are identical to those of Device Example 1, utilizing the same substrate and electrode materials, with the same electrode thickness. The only difference is the material used in the light-emitting layer. The layer structures and test results for each device example are shown in Tables 3 and 4, respectively.

[0160] Device Example 1

[0161] like Figure 1 As shown, the transparent substrate layer 1 is a transparent PI film, and the ITO anode layer 2 (film thickness is 150nm) is washed, that is, washed with a detergent (Semiclean M-L20), washed with pure water, dried, and then washed with ultraviolet-ozone to remove organic residues on the surface of the transparent ITO. On the ITO anode layer 2 after the above washing, a vacuum evaporation device is used to evaporate HT-1 and HI-1 with a film thickness of 10nm as the hole injection layer 3, and the mass ratio of HT-1 and HI-1 is 97:3. Then, HT-1 with a thickness of 60nm is evaporated as the hole transport layer 4. Subsequently, EB-1 with a thickness of 30nm is evaporated as the electron blocking layer 5. After the above-mentioned electron blocking material is evaporated, the light-emitting layer 6 of the OLED light-emitting device is made, using CBP as the main material and compound 1 as the doping material. The mass ratio of CBP and compound 1 is 97:3, and the light-emitting layer thickness is 30nm. After the light-emitting layer 6, HB-1 was vacuum-deposited to a thickness of 5 nm. This layer served as the hole-blocking layer 7. After the hole-blocking layer 7, ET-1 and Liq were vacuum-deposited in a 1:1 weight ratio to form a 30 nm thick film. This served as the electron-transporting layer 8. On the electron-transporting layer 8, a 1 nm thick LiF layer was vacuum-deposited. This served as the electron-injection layer 9. On the electron-injection layer 9, an 80 nm thick Mg:Ag electrode layer was vacuum-deposited in a 1:9 weight ratio. This served as the cathode layer 10.

[0162] The following describes in detail the application effects of the OLED materials synthesized by the present invention in devices using device Examples 10-18 and Comparative Examples 4-6. The device fabrication processes for Device Examples 11-18 and Comparative Examples 4-6 are identical to those for Device Example 10, utilizing the same substrate and electrode materials, with the same electrode thickness. The only difference is the material used in the light-emitting layer. The layer structures and test results for each device example are shown in Tables 3 and 4, respectively.

[0163] Device Example 10

[0164] The transparent substrate layer 1 is a transparent PI film. The ITO anode layer 2 (film thickness 150nm) is washed, that is, washed with a detergent (Semiclean M-L20), washed with pure water, dried, and then washed with ultraviolet-ozone to remove organic residues on the transparent ITO surface. On the ITO anode layer 2 after the above washing, HT-1 and HI-1 are evaporated with a film thickness of 10nm as the hole injection layer 3 using a vacuum evaporation device. The mass ratio of HT-1 to HI-1 is 97:3. HT-1 is then evaporated with a thickness of 60nm as the hole transport layer 4. EB-1 is then evaporated with a thickness of 30nm as the electron blocking layer 5. After the above electron blocking material evaporation is completed, the light-emitting layer 6 of the OLED light-emitting device is prepared. CBP and DMAC-BP are used as the dual host materials, and compound 1 is used as the dopant material. The mass ratio of CBP, DMAC-BP and compound 1 is 67:30:3, and the light-emitting layer thickness is 30nm. After the light-emitting layer 6, HB-1 was vacuum-deposited to a thickness of 5 nm. This layer served as the hole-blocking layer 7. After the hole-blocking layer 7, ET-1 and Liq were vacuum-deposited in a 1:1 weight ratio to form a 30 nm thick film. This served as the electron-transporting layer 8. On the electron-transporting layer 8, a 1 nm thick LiF layer was vacuum-deposited. This served as the electron-injection layer 9. On the electron-injection layer 9, an 80 nm thick Mg:Ag electrode layer was vacuum-deposited in a 1:9 weight ratio. This served as the cathode layer 10.

[0165] The molecular structure formula of the relevant materials is shown below:

[0166]

[0167] After completing the OLED light-emitting device as described above, the anode and cathode were connected using a known drive circuit, and the device's current efficiency, external quantum efficiency, and lifetime were measured. Examples and comparative examples of devices prepared using the same method are shown in Table 3; the test results for the current efficiency, external quantum efficiency, and lifetime of the resulting devices are shown in Table 4.

[0168] Table 3

[0169]

[0170]

[0171] Table 4

[0172]

[0173]

[0174] Note: Voltage, current efficiency, and luminescence peak were measured using an IVL (current-voltage-luminance) test system (Suzhou Fushida Scientific Instrument Co., Ltd.); the lifespan test system was an EAS-62C OLED device lifespan tester from Japan System Giken Co., Ltd.; LT95 refers to the time it takes for the device's luminance to decay to 95%; all data are measured at 10 mA / cm 2 Next test.

[0175] It can be seen from the device data results in Table 4 that, compared with device comparison examples 1-6, the current efficiency, external quantum efficiency and device life of the organic light-emitting device of the present invention are greatly improved compared with OLED devices made of known materials.

[0176] In summary, the above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A boron-containing organic compound as an OLED doping material, characterized in that: The structure of the boron-containing organic compound is shown in general formula (2) or general formula (3): In general formula (2) and general formula (3), Z1-Z8 are represented by CH or C-(R1) in the same or different manner each time they appear; Each occurrence of R1 is identical or different and represents a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C6~C 30 Arylamine, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 heteroaryl; The M1 ring and the M2 ring are independently represented by a substituted or unsubstituted benzene ring, a substituted or unsubstituted benzofuran ring, or a substituted or unsubstituted benzothiophene ring; X1, X2, X3, X4 each appear identically or differently and are represented by O, S or N-(R2); Each occurrence of R2 is identical or different and represents a substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 heteroaryl; The substituents of the "substituted or unsubstituted" groups are selected from deuterium, halogen, C1-C 10 Alkyl, C3~C 10 Cycloalkyl, C6~C 30 Aryl, C2~C 30 Heteroaryl, C6~C 30 Aryl or C2~C 30 Heteroaryl-substituted amine, deuterium-substituted C1~C 10 Alkyl, deuterium substituted C3~C 10 Any of cycloalkyl; The heteroatoms in the heteroaryl group are selected from one or more of oxygen, sulfur, boron and nitrogen atoms.

2. A boron-containing organic compound as an OLED doping material, characterized in that: The structure of the boron-containing organic compound is shown in any one of the general formulas (1-1) to (1-6): In general formula (1-1) to general formula (1-6), Z1-Z8 are represented by CH or C-(R1) in the same or different manner each time; Each occurrence of R1 is identical or different and represents a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C6~C 30 Arylamine, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 heteroaryl; X1, X2, X3, X4 each appear identically or differently and are represented by O, S or N-(R2); Each occurrence of R2 is identical or different and represents a substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 heteroaryl; X5 and X6 are represented by O, S or N-(R3) in the same or different manner at each occurrence; Each occurrence of R3 is identical or different and represents a substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 heteroaryl; R a 、R b 、R c 、R d Each occurrence is represented identically or differently by deuterium, halogen, C1~C 10 Alkyl, C3~C 10 Cycloalkyl, C6~C 30 Aryl, C2~C 30 Heteroaryl, C6~C 30 Aryl or C2~C 30 Heteroaryl-substituted amine, deuterium-substituted C1~C 10 Alkyl, deuterium substituted C3~C 10 Cycloalkyl; m, n, s, and k are independently represented as 0, 1, 2, 3, and 4; The substituents of the "substituted or unsubstituted" groups are selected from deuterium, halogen, C1-C 10 Alkyl, C3~C 10 Cycloalkyl, C6~C 30 Aryl, C2~C 30 Heteroaryl, C6~C 30 Aryl or C2~C 30 Heteroaryl-substituted amine, deuterium-substituted C1~C 10 Alkyl, deuterium substituted C3~C 10 Any of cycloalkyl; The heteroatoms in the heteroaryl group are selected from one or more of oxygen, sulfur, boron and nitrogen atoms.

3. The boron-containing organic compound according to claim 1, characterized in that The structure of the boron-containing organic compound is shown in any one of the general formulas (4-1) to (4-8): In the general formula (4-1) and the general formula (4-8), the definitions of Z1 to Z8, M1 ring, M2 ring, and R2 are the same as those in claim 1.

4. The boron-containing organic compound according to claim 1, characterized in that The M1 ring and the M2 ring are represented by the following ring structures: Asterisks indicate sites where rings can be fused.

5. The boron-containing organic compound according to claim 1, characterized in that R1 represents deuterium, a fluorine atom, a cyano group, an adamantyl group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted diphenylamino group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted quinolyl, substituted or unsubstituted furyl, substituted or unsubstituted thienyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted triazinyl, substituted or unsubstituted methoxy; R2 represents adamantyl, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted isopropyl, substituted or unsubstituted isobutyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted furyl, substituted or unsubstituted thienyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl; The substituents for the above-mentioned substitutable groups may be selected from deuterium, a fluorine atom, an adamantyl group, a methyl group, a deuterated methyl group, an ethyl group, a deuterated ethyl group, an isopropyl group, a deuterated isopropyl group, a tert-butyl group, a deuterated tert-butyl group, an isobutyl group, a deuterated cyclopentyl group, a cyclopentyl group, a diphenylamino group, a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyridyl group, a quinolyl group, a furyl group, a thienyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, an N-phenylcarbazolyl group, a xanthone group, an azadimethylfluorenyl group, and an azadiphenylfluorenyl group.

6. The boron-containing organic compound according to claim 2, characterized in that R1 represents deuterium, a fluorine atom, a cyano group, an adamantyl group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted diphenylamino group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted quinolyl, substituted or unsubstituted furyl, substituted or unsubstituted thienyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted triazinyl, substituted or unsubstituted methoxy; R a 、R b 、R c 、R d Deuterium, fluorine atom, adamantyl, methyl, ethyl, isopropyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, biphenyl, terphenyl, diphenylamino, naphthyl, anthracenyl, phenanthrenyl, pyridyl, quinolyl, furyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, 9,9-dimethylfluorenyl, triazinyl; R2 and R3 represent adamantyl, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted isopropyl, substituted or unsubstituted isobutyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted furyl, substituted or unsubstituted thienyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl; The substituents for the above-mentioned substitutable groups may be selected from deuterium, a fluorine atom, an adamantyl group, a methyl group, a deuterated methyl group, an ethyl group, a deuterated ethyl group, an isopropyl group, a deuterated isopropyl group, a tert-butyl group, a deuterated tert-butyl group, an isobutyl group, a deuterated cyclopentyl group, a cyclopentyl group, a diphenylamino group, a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyridyl group, a quinolyl group, a furyl group, a thienyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, an N-phenylcarbazolyl group, a xanthone group, an azadimethylfluorenyl group, and an azadiphenylfluorenyl group.

7. A boron-containing organic compound as an OLED doping material, characterized in that: The specific structural formula of the boron-containing organic compound is any one of the following structures:

8. An organic light-emitting device comprising a cathode, an anode, and a functional layer, wherein the functional layer is located between the cathode and the anode, characterized in that: The functional layer of the organic light-emitting device comprises the boron-containing organic compound according to any one of claims 1 to 7.

9. The organic light-emitting device according to claim 8, wherein the functional layer comprises a light-emitting layer, The doping material of the light-emitting layer is the boron-containing organic compound according to any one of claims 1 to 7.

10. The organic light-emitting device according to claim 8, wherein the light-emitting layer comprises a first host material, a second host material and a doping material, wherein: At least one of the first host material and the second host material is a TADF material, and the doping material is the boron-containing organic compound according to any one of claims 1 to 7.

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